Trichlorostyrene and method of preparing the same



Patented July 21, 1942 TRICHLOROSTYRENE AND METHOD OF PREPARING THE SAME Arthur A. Levine and Oliver W. Cass, Niagara Falls, N. Y., assignors to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application March 18,1940,

Serial No. 324,616

7 Claims.

This invention relates to the preparation of valuable chlorinated aromatic compounds. More particularly, it relates to the preparation of trichlorostyrene from ethyltrichlorobenzene as a starting material. The present application is a continuation-in-part of our copending application Serial No. 136,024, filed April 9, 1937, which is directed to the preparation of pentachlorostyrene from ethylpentachlorobenzene.

Ethyl'trichlorobenzene is readily prepared by the nuclear chlorination of ethylbenzene. The chlorination is carried out in the absence of light and in the presence of a chlorine carrier which is metallic iron. The trichloride is separated by distillation from the ,dichlorides and tetrachlorides which are formed in small amounts. The product thus obtained is a mixture of the six possible isomers of ethyltrichlorobenzene.

Our process for the preparation of trichlorostyrene from ethyltrichlorobenzene involves two steps. In the first step, ethyltrichlorobenzen is reacted with chlorine under conditions such that mono-chlorethyltrichlorobenzene is formed. In the second'step, the mono-chlorethyltrichlorobenzene is converted to trichlorostyrene by splitting ofi hydrogen chloride from the side chain.

Accordingly, one of theobjects of this invention involves the preparation of trichlorostyrene from ethyltrichlorobenzene in satisfactory yield. Another object is the preparation of the desired product, trichlorostyrene, by means of a twostage process involving two separate chemical readded, the yields are decreased due to the formation of higher chlorides. The reaction involved is represented by the following equation:

The mixture of unchanged ethyltrichlorobenzene and chlorethyltrichlorobenzene' may be separated into its constituent by vacuum distillation. In the course of the distillation, it is important that the temperature does not exceed 150 C. as the chlorethyltrichlorobenzene under- M goes decomposition at higher temperatures.

actions. The first of these reactions involves the preparation of mono-chlorethyltrichlorobenzene, and the second, the conversion of that product to trichlorostyrene.

The various isomers of trichlorostyrene represented by the formula CeH2Cl3.CH=CH-2 are believed to be new compounds never before described in the chemical literature. It is, therefore, a further object of this invention to produce these new chemical compounds. Other objects and advantages of the invention will be apparent from the ensuing detailed disclosure.

In order to convert ethyitrichlorobenzene to mono-chlorethyltrichlorobenzene, the ethyltri chlorobenzene starting material may be reacted with chlorine in the presence of light and in the absence of any chlorine carrier until approximately of the amount of chlorine theoretically required for the introduction of one chlorine atom per mole of ethyltrichlorobenzene has been added. This gives a mixture of approximately 50% unchanged ethyltrichlorobenzene and 50% mono-chloroethyltrichlorobenzene. If much more more than 50%of the theoretical chlorine is Trichlorostyrene is most conveniently prepared from the chlorethyltrichlorobenzene simply by distillation at atmospheric pressure. At the temperature of distillation, the chlorine atom in the ethyl side chain is released as hydrogen chloride, converting the 'chlorethyl group to a vinyl group and thus formin trichlorostyrene. The reaction is as follows:

Alternatively the chlorethyltrichlorobenzene may beconverted to trichlorostyrene by treatment of the former with a base as, for example, alcoholic potassium hydroxide, or the removal of one molecule of HCl from the chlorethyl side chain of chlorethyltrichlorobenzene may be effected by means of any of the other usual dehydrohalogenation treatments known in the art.

The invention may be further illustrated by the specific procedure described in the following example:

EXAMPLE Preparation of ethyltrichlorobenzene scrubbing system for absorbing the evolved hydrogen chloride. Iron filings in the amount of grams were then added to the flask and operationlof the stirrer begun. Chlorine gas was r then passed in and the temperature of the regrams (31.6 moles) of hydrogen chloride had been absorbed by the scrubbing system the chlorination was stopped. The amount of chlorine absorbed corresponded to 2.93 moles of chlorine for each mole of ethylbenzene. The reaction mixture was then decanted i'rom the iron catalyst, washed once with water, once with a 1 solution of sodium bicarbonate, again with water and then dried.

The major portion of the product, when distilled, was found to have boiling points within the range 235 to 250' C. This fraction consisted principally of the various isomers of ethyltrichlorobenzene.

chlorethrltrichlorobenzene 838 grams (4 moles) of ethyltrichlorobenzene was charged into a reaction vessel equipped with a stirrer, a chlorine inlet tube, a thermometer, and a reflux condenser leading to a hydrogen chloride trap containing water. The reaction vessel was illuminated by means or an incandescent lamp.

The ethyltrichlorobenzene was then heated to about MiG-120 C. and 150 grams (2.1 moles) of chlorine was gradually introduced. During the course of the reaction, '13 grams of hydrogen chloride was evolved and the gain in weight or the contents of the flask was approximately '12 grams. Y

The reaction mixture was then vacuum-disency to polymerize under the action or. either light or heat.

, Because otits stability, low melting point and other desirable properties, triehlorostyrenc is ad pted for use either alone or in combination with othermaterials ior such varied purposes as dielectric media for electrical apparatus, media for transferring heat at elevated temperatures, brake fluids and hydraulic brake systems, extreme pressure lubricants, absorbents in scrubbing systems,,cooling agents for internal combustion agents. etc.

It is to be understood that our invention-is not restricted to the specific embodiments described hereinabove, but includes all such modifications, variations, and equivalents, as fall withlnthc scope oi the appended claims.

tilled-under an absolute pressure 0110 mm. oi

mercury. The portion distilling below a temperature of 127 C. consisted principally of unchanged ethyltrichlorobenzene. The fraction distilling between 130 and 152 0. consisted essentially or a mixture of the isomers of mono-chlorethyltrichlorobenzene. The product had a density of 1.445 at 20 C. and a melting point below --40 C.

Conversion of mono-chlorethyltrichlorobenzene to trichlorosturene The mixture of mono-chlorethyltrichlorobenzene isomers, as obtained by the procedure described above, was distilled at atmospheric pressure, then re-distilled a second and third time, and finally blown with air until no iurther hydrogen chloride could be removed. The final We claim:

1. A process ior preparing trichlorostyrene which comprises chlorinating eth'yltrichlorobenzene to form monochlorethyltrichlorobenzene and subjecting said monochlorethyltrichlorobenzone to dehydrochlorination conditions, thereby removing one mole oihydrogen chloride and iorming trichlorostyrene.

2. A process for preparing trichlorostyrene which comprises reacting ethyltrichlorobenzene with chlorine in the absence 0! a halogenation catalyst, but in the presence or light, to form mono-chlorethyltrichlorobenzene and then subiecting said mono-chlorethyltrichlorobenzene to dehydrochlorination conditions to form trichlorostyrene.

3. A process of preparing trichlorostyrene which comprises reacting ethyltrichlorobenzene with chlorine in the absence'oi a halogenation catalyst, but in the presence oi light to form mono-chlorethyltrichlorobenzene and then pyrolytically decomposing said monochlorethyltrichlorobenzene to form trichlorostyrene.

4. A process for preparing trichlorostyrene from mono-chlorethyltrichlorobenzene which comprises subjecting said mono-chlorethyltrichlorobenzene to dehydrochlorination conditions, thereby removing one mole of hydrogen chloride per pole of mono-chlorethyltrichlorobenzene.

5. A process for preparing trichlo'rostyrene which comprises subjecting mono-chlorethyltrichlorobenzene to thermodecomposition, thereby removing one mole of hydrogen chloride per mole of mono-chlorethyltrichlorobenzene.

6. Trichlorostyrene.

7. A composition comprising essentially mixed isomers of trichlorostyr'ene.

' ARTHUR A. LEVINE.

OLIVER W. CASS. 

